Coating compositions containing 1,3,5-triazine compounds substituted with acetal and/or cyclized acetal-based groups

ABSTRACT

Coating compositions containing new classes of 1,3,5-triazine compounds as crosslinkers are disclosed, which compounds are of the general formula ##STR1## wherein each of Y, Z, and optionally X are independently selected from a group of the formula (II), (III) and/or (IV) ##STR2## and wherein A, D, Q, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7  and R 8  are as defined herein.

This application is a divisional of copending U.S. application Ser. No.08/408,323, filed Mar. 21, 1995, now U.S. Pat. No. 5,612,703, which isincorporated by reference herein for all purposes as if fully set forth.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the preparation of compounds and compositionswhich are particularly suitable for use as crosslinking agents incurable compositions, and especially coatings, which are capable ofcuring at lower temperatures, and which do not release formaldehyde as avolatile by-product when cured.

2. Description of Related Art

Various derivatives of amino-1,3,5-triazines are described in theliterature as being utilized in a wide variety of fields. An importantuse of some triazine derivatives, such as the alkoxyalkyl derivatives ofmelamine and guanamine, is based upon their ability to act ascrosslinking agents in curable compositions containing resins whichcontain active hydrogen groups. While alkoxyalkylated melamines andguanamines provide excellent results in some respects, they do have thedisadvantage of releasing formaldehyde as a volatile by-product undercure conditions. Because of this, it has long been a desire of industryto find acceptable alternatives which do not emit formaldehyde duringcure.

A recently discovered non-formaldehyde alternative which has shown greatpromise is the class of isocyanate and carbamate-functional1,3,5-triazine crosslinking agents disclosed in the commonly owned U.S.Pat. Nos. 4,939,213, 5,084,541 and 5,288,865, which are incorporated byreference herein for all purposes as if fully set forth. The isocyanateand carbamate functional 1,3,5-triazines disclosed therein are efficientnon-formaldehyde emitting crosslinking agents which are particularlyuseful in curable coating compositions.

Another non-formaldehyde alternative which utilizes addition chemistryin crosslinking polyfunctional active hydrogen containing compounds isthe class of 2,4,6-tris-lactam substituted 1,3,5-triazine crosslinkingagents disclosed in EP-A-0570563, which is also incorporated byreference herein for all purposes as if fully set forth. The tris-lactamcrosslinkers disclosed therein are efficient non-formaldehyde emittingcrosslinking agents which are particularly useful in curable powdercoating compositions.

Still another alternative is described in U.S. Pat. No. 4,647,611, U.S.Pat. No. 4,663,410, U.S. Pat. No. 4,691,026, U.S. Pat. No. 4,774,283,U.S. Pat. No. 4,788,288, U.S. Pat. No. 4,814,226, U.S. Pat. No.4,864,055, U.S. Pat. No. 4,959,489, U.S. Pat. No. 5,298,567,EP-A-0218827, an article by R. K. Pinschmidt, Jr., et al. in Amer. Chem.Soc. Symp. Ser., Crosslinked Polymers, Volume 367, page 453 (1988) andan article by K. Kjellqvist et al. in J. Appi. Polym. Science, Volume51, page 1063 (1994), all of which are also incorporated herein byreference for all purposes as if fully set forth. These referencesdisclose N-olefinically unsaturated ketals and acetals, and polymers andcopolymers thereof, usable as non-formaldehyde generating crosslinkingagents.

While some of these systems have shown great promise, the searchcontinues for additional crosslinkers which emit little or noformaldehyde during cure.

We have now discovered new classes of compounds which are preparedwithout formaldehyde, and which function as highly compatiblecrosslinking agents. Films having good appearance, solvent resistanceand gloss characteristics can be produced from coating compositionsutilizing the crosslinking agents in accordance with the presentinvention. Certain of these crosslinkers may additionally produce fullycured films at very low temperatures, typically in the range of fromabout 50° C. to about 90° C. (although higher temperatures may also beutilized), without the need for catalysts (although catalysts may alsobe utilized) such as acids often required for amine- formaldehydecrosslinkers.

SUMMARY OF THE INVENTION

As indicated above, the present invention relates to compounds andcompositions suitable for use as highly resin-compatible crosslinkingagents which do not emit formaldehyde as a volatile by-product duringcure.

The present inventive compounds may be represented by the followingformula (I): ##STR3## wherein X is selected from the group consisting ofhydrogen, halogen, alkyl, aralkyl, aryl, alkoxy, aralkoxy, aryloxy,alkylthio, aralkylthio, arylthio, amido, sulfonamido, sulfonate, amino,a group of the formula (II), a group of the formula (III), and a groupof the formula (IV) ##STR4## wherein A is an alkylene group,

R¹ is selected from the group consisting of hydrogen and a hydrocarbyl,

R² is selected from the group consisting of hydrogen, a hydrocarbyl,--OR⁹ and --SR¹⁰,

R³ is selected from the group consisting of hydrogen, a hydrocarbyl,--OR⁹ and --SR¹⁰, and

R⁴ is selected from the group consisting of --OR¹¹ and --SR¹²,

with the proviso that at least one of R² and R³ is selected from thegroup consisting of --OR⁹ and --SR¹⁰, ##STR5## wherein D is an alkylenegroup,

R⁵ is selected from the group consisting of hydrogen, a hydrocarbyl,--OR⁹ and --SR¹⁰, and

R⁶ is selected from the group consisting of hydrogen, a hydrocarbyl,--OR⁹ and --SR¹⁰,

with the proviso that at least one of R⁵ and R⁶ is selected from thegroup consisting of --OR⁹ and --SR¹⁰, ##STR6## wherein Q is an alkylenegroup,

R⁷ is selected from the group consisting of hydrogen, a hydrocarbyl,--OR⁹ and --SR¹⁰, and

R⁸ is selected from the group consisting of hydrogen and a hydrocarbyl,

wherein

each R⁹ is independently selected from the group consisting of hydrogenand a hydrocarbyl, or together with R¹¹ forms a hydrocarbylene group,

each R¹⁰ is a hydrocarbyl, or together with R¹² forms a hydrocarbylenegroup,

each R¹¹ is independently selected from the group consisting of hydrogenand a hydrocarbyl, or together with R⁹ forms a hydrocarbylene group,

each R¹² is a hydrocarbyl, or together with R¹⁰ forms a hydrocarbylenegroup,

with the proviso that, other than in a group of the formula (II), (III)or (IV), X contains no olefinic unsaturation; and

wherein

each of Y and Z is independently selected from the group consisting of agroup of the formula (II), a group of the formula (III) and a group ofthe formula (IV).

This invention also includes a process for preparing derivatives of1,3,5-triazines, including those of the formula (I) described above,which process comprises the step of contacting:

(i) a 1,3,5-triazine derivative represented by the formula (V) or anoligomer thereof: ##STR7## wherein L¹ is selected from the groupconsisting of hydrogen, halogen, alkyl, aralkyl, aryl, alkoxy, aralkoxy,aryloxy, alkylthio, aralkylthio, arylthio, amido, sulfonamido,sulfonate, amino and a leaving group not previously mentioned, and

each of L² and L³ is independently a leaving group; and

(ii) a nucleophilic reagent selected from the group consisting of acompound of the formula (VI), a compound of the formula (VII), acompound of the formula (VIII), a salt thereof and mixtures thereof:##STR8## wherein

R¹ -R¹², A, D and Q are as defined above, and

wherein said contacting is carried out at a temperature and length oftime sufficient to produce a 1,3,5-triazine derivative having thereon onaverage at least two groups derived from the nucleophilic reagent.

The present invention further includes a process for preparingderivatives of 1,3,5-triazines, including those of the formula (I)described above containing groups of the formula (III), which processcomprises the steps of (a) contacting (i) a 1,3,5-triazine derivativerepresented by the formula (V) or an oligomer thereof, with (ii) anucleophilic reagent of the formula (VI) or a salt thereof, at atemperature and length of time sufficient to produce a 1,3,5-triazinederivative having thereon on average at least two open-chain groupsderived from the nucleophilic agent; then (b) intramolecularly cyclizingat least a portion of the open-chain groups.

The present invention further includes a process for preparingderivatives of 1,3,5-triazines, including those of the formula (I)described above containing groups of the formula (IV), which processcomprises the step of eliminating from a 1,3,5-triazine derivative ofthe formula (I) containing a group of the formula (III), the element ofHOR⁹ from the group of the formula (III).

The present invention also relates to compositions obtainable by theprocesses as described above. Such compositions may comprise a complexmixture of compounds, including but not limited to compounds of theformula (I) as well as oligomeric versions thereof, but which in anyevent contain on average at least two groups of the formula (II), (III)and/or (IV) per molecule. Oligomers of the compounds of the formula (I),wherein X is a leaving group, may also be prepared by reacting such witha compound containing at least two active hydrogen groups, such as adiol or polyol, or diamine or polyamine.

The present invention further includes a curable composition,comprising: (a) a crosslinker component comprising the 1,3,5-triazinecompound of the formula (I); and (b) a polyfunctional materialcontaining on average at least two groups with active hydrogenfunctionality and/or functionality convertible thereto. The compositionsprepared by the processes described above, of course, may function asthe crosslinker component since they comprise compositions of theformula (I).

The present invention also relates to coating compositions based uponthe above curable compositions, methods for coating substrates with suchcoating compositions, substrates so coated therewith, crosslinked filmsor objects derived from the curable compositions, and various end usesthereof.

Unlike hydroxyalkylated and alkoxyalkylated aminoplast derivedcrosslinking agents which (i) are prepared using formaldehyde, (ii)contain varying levels of free formaldehyde, and (iii) releaseformaldehyde during cure, the crosslinkers of the present invention havethe advantage of containing no functionality capable of releasingformaldehyde during heat cure. Certain of the present crosslinkers, andparticularly those containing cyclic groups of the formula (III), alsohave the advantage of producing coatings which may be fully cured atvery low temperatures, typically in the range of about 50° C. to about90° C. (although higher temperatures may also be utilized), without theneed to use cure catalysts (although such may also be used). Cured filmshaving good appearance, excellent thermal and ultraviolet (UV) lightstability, good outdoor weatherability, good solvent resistance and highgloss can be produced from such coatings.

These and other features and advantages of the present invention will bemore readily understood by those skilled in the relevant art from areading of the following detailed description.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As indicated above, the present invention relates most broadly tocompounds of the formula (I). In this formula (I), and in the broadestcontext of the present invention, the following terms are given themeanings as set forth below:

"Alkyl" includes, for example, linear, branched, cyclic and alkylsubstituted cyclic alkyls.

"Aryl" includes, for example, phenyl, other aryls as well as alkylsubstituted aryls (alkaryl).

"Amido" includes, for example, both substituted and unsubstitutedamidos, such as alkyl and/or aryl substituted amido groups.

"Amino" includes, for example, amino, alkyl and/or aryl substitutedaminos, and heterocyclic N-containing groups optionally containing adifferent heteroatom in the ring structure. As examples of non-cyclicamino groups may be mentioned an amino group, a monoalkylamino, amonoaralkylamino, a monoarylamino, a dialkylamino, a diaralkylamino anda diarylamino. As examples of the cyclic amino groups may be mentionedsubstituted and unsubstituted pyrrolidino, piperidino, azepino,piperizino and morpholino groups.

"Hydrocarbyl" broadly refers to a group which contains at least carbonand hydrogen atoms and includes, for example, alkyl, aryl, aralkyl,alkenyl, and substituted derivatives thereof.

Preferred compounds of the general formula (I) are those wherein:

X is selected from the group consisting of hydrogen, alkyl of 1 to 8carbon atoms, aryl of 6 to 10 carbon atoms, aralkyl of 7 to 14 carbonatoms, alkoxy of 1 to 8 carbon atoms, aryloxy of 6 to 10 carbon atoms,aralkoxy of 7 to 14 carbon atoms, alkylthio of 1 to 8 carbon atoms,arylthio of 6 to 10 carbon atoms, aralkylthio of 7 to 14 carbon atoms,amido of 1 to 8 carbon atoms, sulfonamido of 1 to 8 carbon atoms, amino(--NH₂), monoalkylamino of 1 to 8 carbon atoms, dialkylamino of 2 to 16carbon atoms, pyrrolidino, piperidino, azepino, morpholino,N-alkylpiperazino, a group of the formula (II), a group of the formula(III) and a group of the formula (IV);

more preferably selected from the group consisting of a group of theformula (II), a group of the formula (III) and a group of the formula(IV), and especially selected from the group consisting of a group ofthe formula (II) and a group of the formula (III);

A is an alkylene group of 1 to 8 carbon atoms, and more preferably analkylene group of 3 to 8 carbon atoms, and especially an alkylene groupof 3 to 5 carbon atoms;

R¹ is selected from the group consisting of hydrogen and an alkyl of 1to 8 carbon atoms;

R² is selected from the group consisting of hydrogen, an alkyl of 1 to 8carbon atoms and --OR⁹ ;

R³ is selected from the group consisting of hydrogen, an alkyl of 1 to 8carbon atoms and --OR⁹ ;

R⁴ is --OR¹¹,

with the proviso that at least one of R² and R³ is a group --OR⁹, andespecially only one of R² and R³ is a group --OR⁹ ;

D is an alkylene group of 3 to 8 carbon atoms, and more preferably analkylene group of 3 to 5 carbon atoms;

R⁵ is selected from the group consisting of hydrogen, an alkyl of 1 to 8carbon atoms and --OR⁹ ;

R⁶ is selected from the group consisting of hydrogen, a an alkyl of 1 to8 carbon atoms and --OR⁹ ;

with the proviso that at least one of R⁵ and R⁶ is --OR⁹, and especiallyonly one of R⁵ and

R⁶ is a group --OR⁹ ;

Q is an alkylene group of 2 to 7 carbon atoms, more preferably analkylene group of 2 to 4 carbon atoms;

R⁷ is selected from the group consisting of hydrogen, an alkyl of 1 to 8carbon atoms and --OR⁹, and more preferably selected from hydrogen andan alkyl of 1 to 8 carbon atoms;

R⁸ is selected from the group consisting of hydrogen and an alkyl of 1to 8 carbon atoms;

each R⁹ is independently selected from the group consisting of hydrogenand an alkyl of 1 to 8 carbon atoms, or together with R¹¹ forms analkylene group of 2 to 8 carbon atoms,

each R¹¹ is independently selected from the group consisting of hydrogenand an alkyl of 1 to 8 carbon atoms, or together with R⁹ forms analkylene group of 2 to 8 carbon atoms,

with the proviso that, other than in a group of the formula (II), (III)or (IV), X contains no olefinic unsaturation; and

each of Y and Z is independently selected from the group consisting of agroup of the formula (II), a group of the formula (III) and a group ofthe formula (IV), and more preferably selected from the group consistingof a group of the formula (II) and a group of the formula (III).

Particularly preferred compounds of the general formula (I) are thosewherein:

X is selected from the group consisting of hydrogen, alkyl of 1 to 8carbon atoms, aryl of 6 to 10 carbon atoms, aralkyl of 7 to 14 carbonatoms, alkoxy of 1 to 8 carbon atoms, aryloxy of 6 to 10 carbon atoms,aralkoxy of 7 to 14 carbon atoms, alkylthio of 1 to 8 carbon atoms,arylthio of 6 to 10 carbon atoms, aralkylthio of 7 to 14 carbon atoms,amido of 1 to 8 carbon atoms, sulfonamido of 1 to 8 carbon atoms, amino(--NH₂), monoalkylamino of 1 to 8 carbon atoms, dialkylamino of 2 to 16carbon atoms, pyrrolidino, piperidino, azepino, morpholino,N-alkylpiperazino, a group of the formula (II), a group of the formula(III) and a group of the formula (IV);

more preferably selected from the group consisting of a group of theformula (II), a group of the formula (III) and a group of the formula(IV), and especially selected from the group consisting of a group ofthe formula (II) and a group of the formula (III);

A is an alkylene group of 3 to 5 carbon atoms;

R¹ is selected from the group consisting of hydrogen and an alkyl of 1to 4 carbon atoms;

R² is --OR⁹ ;

R³ is selected from the group consisting of hydrogen and an alkyl of 1to 4 carbon atoms;

R⁴ is --OR¹¹ ;

D is an alkylene group of 3 to 5 carbon atoms;

R⁵ is --OR⁹ ;

R⁶ is selected from the group consisting of hydrogen and an alkyl of 1to 4 carbon atoms;

Q is an alkylene group of 2 to 4 carbon atoms;

R⁷ is selected from the group consisting of hydrogen and an alkyl of 1to 8 carbon atoms;

R⁸ is selected from the group consisting of hydrogen and an alkyl of 1to 4 carbon atoms;

each R⁹ is independently selected from the group consisting of hydrogenand an alkyl of 1 to 4 carbon atoms, or together with R¹¹ forms analkylene group of 2 to 8 carbon atoms,

each R¹¹ is independently selected from the group consisting of hydrogenand an alkyl of 1 to 4 carbon atoms, or together with R⁹ forms analkylene group of 2 to 8 carbon atoms,

with the proviso that, other than in a group of the formula (II), (III)or (IV), X contains no olefinic unsaturation; and

each of Y and Z is independently selected from the group consisting of agroup of the formula (II), a group of the formula (III) and a group ofthe formula (IV), and more preferably selected from a group of theformula (II) and a group of the formula (III).

Process for Preparing the Compounds of the Formula (I) and CompositionsContaining Such Compounds

The compounds of the formula (I) may be prepared by contactingcomponents (i) and (ii) as earlier described.

In the practice of the process of the invention, contacting may becarried out by adding (ii) to (i) and heating the reaction mixture for atemperature and time sufficient to displace at least two leaving groupspresent on (i) and substituting therefor at least two groups derivedfrom (ii). In a preferred procedure, (i) and (ii) are initiallycontacted at temperatures in the range of from about 0° C. to about 50°C. for an initial exothermic reaction, after which the temperature ismaintained in the range of from about 50° C. to about 150° C. for thefinal stages of reaction to effect complete conversion. The reactiontime is typically in the range of from about 15 minutes to about 120minutes for the initial exothermic reaction, and thereafter it is in therange of from about 2 hours to about 24 hours for the final stages ofreaction to effect complete conversion.

The 1,3,5-triazine derivatives (i) of the formula (V) are generallyknown compounds, and preferably include those wherein:

L¹ is selected from the group consisting of hydrogen, alkyl, aralkyl,aryl and a leaving group selected from halogen, alkoxy, aralkoxy,aryloxy, alkylthio, aralkylthio, arylthio, amino, amido, sulfonamido andsulfonate, and

each of L² and L³ is independently a leaving group selected fromhalogen, alkoxy, aralkoxy, aryloxy, alkylthio, aralkylthio, arylthio,amino, amido, sulfonamido and sulfonate.

Especially preferred are those wherein L¹, L² and L³ are eachindependently a halogen, and particularly chloride (cyanuric chloride).

The nucleophilic reagents (ii) are also generally known compounds asexemplified, for example, in previously incorporated U.S. Pat. No.4,647,611, U.S. Pat. No.4,663,410, U.S. Pat. No. 4,691,026, U.S. Pat.No. 4,774,283, U.S. Pat. No. 4,788,288, U.S. Pat. No. 4,814,226, U.S.Pat. No. 4,864,055, U.S. Pat. No. 4,959,489, U.S. Pat. No. 5,298,567,EP-A-0218827, the article by R. K. Pinschmidt, Jr., et al. in Amer.Chem. Soc. Symp. Ser., Crosslinked Polymers, Volume 367, page 453 (1988)and the article by K. Kjellqvist et al. in J. AppI. Polym. Science,Volume 51, page 1063 (1994).

As specific examples of compounds of the formula (VI) may be mentionedaminoacetaldehyde dimethyl acetal, aminoacetaldehyde diethyl acetal,aminoacetaldehyde dipropyl acetal, aminoacetaldehyde diisopropyl acetal,aminoacetaldehyde dibutyl acetal, aminoacetaldehyde diamyl acetal,aminoacetaldehyde methylethyl acetal, 3-aminopropionaldehyde dimethylacetal, 3-aminopropionaldehyde diethyl acetal, 3-aminopropionaldehydedipropyl acetal, 3-aminopropionaldehyde diisopropyl acetal,3-aminopropionaldehyde dibutyl acetal, 3-aminopropionaldehyde diamylacetal, 3-aminopropionaldehyde methylethyl acetal, 4-aminobutryaldehydedimethyl acetal, 4-aminobutryaldehyde diethyl acetal,4-aminobutryaldehyde dipropyl acetal, 4-aminobutryaldehyde diisopropylacetal, 4-aminobutryaldehyde dibutyl acetal, 4-aminobutryaldehyde diamylacetal, 4-aminobutryaldehyde methylethyl acetal, 5-aminopentanaldimethyl acetal, 5-aminopentanal diethyl acetal, 5-aminopentanaldipropyl acetal, 5-aminopentanal diisopropyl acetal, 5-aminopentanaldibutyl acetal, 5-aminopentanal diamyl acetal, 5-aminopentanalmethylethyl acetal, 6-aminohexanal dimethyl acetal, 6-aminohexanaldiethyl acetal, 6-aminohexanal dipropyl acetal, 6-aminohexanaldiisopropyl acetal, 6-aminohexanal dibutyl acetal, 6-aminohexanal diamylacetal, 6-aminohexanal methylethyl acetal, 7-aminoheptanal dimethylacetal, 7-aminoheptanal diethyl acetal, 7-aminoheptanal dipropyl acetal,7-aminoheptanal diisopropyl acetal, 7-aminoheptanal dibutyl acetal,7-aminoheptanal diamyl acetal and 7-aminoheptanal methylethyl acetal, aswell as hydrated forms thereof (containing --OH groups).

As specific examples of compounds of the formula (VII) may be mentioned2-methoxypyrrolidine, 2-ethoxypyrrolidine, 2-hydroxyppiperidine,2-methoxypiperidine, 2-ethoxypiperidine and 2-hydroxypiperidine.

As specific examples of compounds of the formula (IV) may be mentioned2,3-dihydropyrrole and 1,2,3,4-tetrahydropyridine.

As indicated above, the compounds of the formula (VI), (VII) and (VIII)may be used as such or in a salt form, such as the hydrohalide saltslike the hydrochloride or hydrobromide salt.

The 1,3,5-triazine derivatives of the formula (I) containing the cyclicgroup of the formula (III) (as well as the cyclic compounds of theformula (VII)) may be additionally prepared by intramolecularlycyclizing the open chain groups of the formula (II) (and compounds ofthe formula (VI)) in a manner similar to that disclosed in thepreviously incorporated references (for example, U.S. Pat. No.4,64,7611, U.S. Pat. No. 4,691,026, U.S. Pat. No. 4,788,288 and U.S.Pat. No. 4,864,055).

Preferably, such cyclization may be effected by contacting the compoundscontaining the open chain groups of the formula (II) (or compounds ofthe formula (VI) with an anhydrous acid catalyst, typically at roomtemperature, for a period of time typically in the range of from about0.5 hours to about 3 hours for complete conversion. Anhydrous acidcatalysts usable in this process include acids such as strongly acidicAMBERLYS® 15 ion-exchange resin, sulfonic acids, mineral acids, Lewisacids and the like. The anhydrous process typically retains the alkoxyfunctionality of R² and/or R³ (as R⁵ and/or R⁶ as the case may be).

Such cyclization may also be effected by contacting the compoundscontaining the open chain groups of the formula (II) (or compounds ofthe formula (VI)) with aqueous acid catalysts, typically at roomtemperature and in the presence of a water miscible solvent such asacetone, dioxane and the like, for a period of time typically in therange of from about 1 hour to about 7 days. Aqueous acid catalystsusable in this process include aqueous solutions of acids such assulfonic acids, perfluorinated acids, carboxylic acids, phosphoricacids, mineral acids and the like. The aqueous process typicallyconverts at least a portion of the alkoxy functionality of R² and/or R³to hydroxyl groups (as R⁵ and/or R⁶ as the case may be). For thisreason, the aqueous process may not be suitable for compounds whereinboth R² and R³ are alkoxy groups, as both such alkoxy groups may beconverted to hydroxyl groups, with the resulting bis-hydroxyl compoundbeing potentially unstable and proceeding further by elimination ofwater to a carbonyl.

The 1,3,5-triazine derivatives containing the unsaturated cyclic groups("enamines") of the formula (IV) (as well as the unsaturated cycliccompounds of the formula (VII)) may be prepared by further reacting thecompounds containing the cyclic groups of the formula (III) (andcompounds of the formula (VII)) by eliminating the elements of analcohol or water, as the case may be. As examples of eliminationpromoters usable in this process may be mentioned the following classesof compounds: carboxylic acid anhydrides, sulfonic acid anhydrides,thionyl halides, sulfuryl halides, phosphorus trihalides, phosphoruspentahalides, phosphorus pentaoxides, phosphorus oxyhalides, molecularsieves, silica gel, alumina, acid catalyst such as ion-exchange resin,sulfonic acids, perfluorinated acids, carboxylic acids, phosphoric acid,mineral acids, Lewis acids, and mixtures thereof.

Products of these Processes

Although the 1,3,5-triazine compounds of the present invention arebroadly described in terms of the specific molecular structure of theformula (I), the compositions actually resulting from theabove-described processes may in fact, in addition to compounds of theformula (I), include a complex mixture of compounds based on a monomericor oligomeric 1,3,5-triazine core which is unsubstituted, partiallysubstituted and/or fully substituted with one or more of the groups(II)-(IV). The requirement of the present invention is that suchcomposition comprise on average at least two such groups (which may bethe same or different), and preferably on average greater than 2 suchgroups, per molecule.

For those compounds of the formula (I) wherein X is a leaving group,such as described above for L¹, oligomers thereof can be produced byreacting the same with a compound containing active hydrogen groups,such as diols, polyols, diamines and polyamines.

Curable Compositions

An important use of the compounds and compositions described herein isbased on their ability to act as crosslinking agents in curablecompositions, and especially those curable compositions which containpolyfunctional materials which have active hydrogen groups. Thecrosslinkers have on average at least two, and preferably on averagemore than two, reactive sites of the formula (II), (III) and/or (IV) permolecule, which are capable of crosslinking active hydrogen containingresins.

As previously mentioned, the reactive group in the 1,3,5-triazinederived crosslinking agents of the invention may be open chain (II) orcyclic (III and/or IV), producing crosslinking agents which are openchain, cyclic, or a combination crosslinker having both types ofreactive groups. Preferred are those containing at least two groups ofthe formula (II) and/or (III), with at least a portion of the groups,and preferably a predominant portion of such groups, being of theformula (III). Further, the crosslinking agent may have only tworeactive sites such as guanamine derivatives, have three reactive sitessuch as melamine derivatives, or have more than three reactive sitessuch as dimeric or higher oligomeric 1,3,5-triazines. All types of theabove described 1,3,5-triazine derived crosslinking agents are usable inthe curable compositions of the invention.

The polyfunctional material of the curable compositions preferablycontains at least one class of a reactive functionality such as hydroxy,carboxy, amino, amido, carbamato, mercapto, or a blocked functionalitywhich is convertible to any of the preceding reactive functionalities.These polyfunctional materials are those which are conventionally usedin aminoresin coatings, and in general are considered well-known tothose of ordinary skill in the relevant art.

Suitable polyfunctional materials include, for example, polyfunctionalhydroxy group containing materials such as polyols, hydroxyfunctionalacrylic resins having pendant or terminal hydroxy functionalities,hydroxyfunctional polyester resins having pendant or terminal hydroxyfunctionalities, hydroxyfunctional polyurethane prepolymers, productsderived from the condensation of epoxy compounds with an amine, andmixtures thereof. Acrylic and polyester resins are preferred. Examplesof the polyfunctional hydroxy group containing materials includeJONCRYL® 500 acrylic resin (S. C. Johnson & Sons, Racine, Wis.), AT-400acrylic resin (Rohm & Haas, Philadelphia, Pa.), CYPLEX®0 1531 polyesterresin (Cytec Industries, West Paterson, N.J.), CARGILL® 3000 and 5776polyester resins (Cargill, Minneapolis, Minn.), TONE® polyester resin(Union Carbide, Danbury, Conn.), K-FLEX® XM-2302 and XM-2306 resins(King Industries, Norwalk, Conn.), CHEMPOL® 11-1369 resin (CookComposites and Polymers (Port Washington, Wis.), CRYLCOAT® 3494 solidhydroxy terminated polyester resin (UCB CHEMICALS USA, Smyrna, Ga.),RUCOTE® 101 polyester resin (Ruco Polymer, Hicksville, N.Y.), JONCRYL®SCX-800-A and SCX-800-B hydroxyfunctional solid acrylic resins (S. C.Johnson & Sons, Racine, Wis.), and the like. Examples ofcarboxyfunctional resins include CRYLCOAT® solid carboxy terminatedpolyester resin (UCB CHEMICALS USA, Smyrna, Ga.). Suitable resinscontaining amino, amido, carbamato or mercapto groups, including groupsconvertible thereto, are in general well-known to those of ordinaryskill in the art and may be prepared by known methods includingcopolymerizing a suitably functionalized monomer with a comonomercapable of copolymerizing therewith.

The curable compositions of the present invention may optionally furthercomprise a cure catalyst. The cure catalysts usable in the presentinvention include sulfonic acids, aryl, alkyl, and aralkyl acidphosphates, aryl, alkyl, and aralkyl acid pyrophosphates, carboxylicacids, sulfonimides, mineral acids, and a mixture thereof. Of the aboveacids, sulfonic acids are preferred when a catalyst is utilized.Examples of the sulfonic acids include benzenesulfonic acid,para-toluenesulfonic acid, dodecylbenzenesulfonic acid,naphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and amixture thereof. Examples of the aryl, alkyl, and aralkyl phosphates andpyrophosphates include phenyl, para-tolyl, methyl ethyl, benzyl,diphenyl, di-para-tolyl, di-methyl, di-ethyl, di-benzyl,phenyl-para-tolyl, methyl-ethyl, phenyl-benzyl phosphates andpyrophosphates. Examples of the carboxylic acids include benzoic acid,formic acid, acetic acid, propionic acid, butyric acid, dicarboxylicacids such as oxalic acid, fluorinated acids such as trifluoroaceticacid, and the like. Examples of the sulfonimides include dibenzenesulfonimide, di-para-toluene sulfonimide, methyl-para-toluenesulfonimide, dimethyl sulfonimide, and the like. Examples of the mineralacids include nitric acid, sulfuric acid, phosphoric acid,poly-phosphoric acid, and the like.

The curable composition may also contain other optional ingredients suchas fillers, light stabilizers, pigments, flow control agents,plasticizers, mold release agents, corrosion inhibitors, and the like.It may also contain, as an optional ingredient, a medium such as aliquid medium to aid the uniform application and transport of thecurable composition. Any or all of the ingredients of the curablecomposition may be contacted with the liquid medium. Moreover, theliquid medium may permit formation of a dispersion, emulsion, invertemulsion, or solution of the ingredients of the curable composition.Particularly preferred is a liquid medium which is a solvent for thecurable composition ingredients. Suitable solvents include aromatichydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, ketones,esters, ethers, amides, alcohols, water, compounds having a plurality offunctional groups such as those having an ether and an ester group, anda mixture thereof.

Preferably, the ratio of the polyfunctional material to the1,3,5-triazine derived crosslinking agent is in the range of from about99:1 to about 0.5:1. Overall, the equivalent ratio of the crosslinker tothe polyfunctional material is preferably in the range of from about 0.8to about 1.2. The weight percent of the cure catalyst, if present, is inthe range of from about 0.01 to about 3.0 wt % based on the weight ofthe crosslinker and polyfunctional material components.

An important use of the above-described curable compositions is in theformulation of coating compositions. The present invention is alsodirected to such coating compositions as well as to methods of coatingsubstrates by applying onto a substrate the coating compositions andheat curing the same.

The present coating compositions may employ a liquid medium such as asolvent, or it may employ solid ingredients as in powder coatings whichtypically contain no liquids. Contacting may be carried out by dipping,spraying, padding, brushing, rollercoating, flowcoating, curtaincoating,electrocoating or electrostatic spraying.

The liquid or powder coating compositions and a substrate to be coatedare contacted by applying the curable composition onto the substrate bya suitable method, for example, by spraying in the case of the liquidcompositions and by electrostatic spraying in the case of the powdercompositions. In the case of powder coatings, the substrate covered withthe powder composition is heated to at least the fusion temperature ofthe curable composition forcing it to melt and flow out and form auniform coating on the substrate. It is thereafter fully cured byfurther application of heat, typically at a temperature in the range ofabout 120° C. to about 220° C. for a period of time in the in the rangeof about 5 minutes to about 30 minutes and preferably for a period oftime in the range of 10 to 20 minutes. In the case of the liquidcompositions, the solvent is allowed to partially evaporate to produce auniform coating on the substrate. Thereafter, the coated substrate isheated in an oven at a temperature up to about 250° C., for a period oftime in the in the range of about 20 seconds to about 14 days andpreferably for a period of time in the range of 10 to 45 minutes toobtain a fully cured film. In a particularly advantageous embodiment,coating compositions formulated with crosslinkers containing groups ofthe formula (III) can be heat cured at lower temperatures preferablyranging from about 50° C. to about 90° C.

The heat cured compositions of this invention may be employed ascoatings in the general areas of coatings such as original equipmentmanufacturing (OEM) including automotive coatings, general industrialcoatings including industrial maintenance coatings, architecturalcoatings, powder coatings, coil coatings, can coatings, wood coatings,and low temperature cure automotive refinish coatings. They are usableas coatings for wire, appliances, automotive parts, furniture, pipes,machinery, and the like. Suitable surfaces include metals such as steeland aluminum, plastics, wood, and glass. The lower temperature curablecompositions of the present invention, as described above, areparticularly well suited for use to refinish automotive parts and tocoat heat sensitive substrates such as plastics and wood which may bealtered or destroyed entirely at the elevated cure temperaturesprevalent in the heat curable compositions of the prior art.

The crosslinkers of the present invention may also be used as bindersfor non-wovens, curable compositions containing them may be used asadhesives, and various formulations thereof may be employed to producecrosslinked molded articles.

The following examples illustrate various specific embodiments of thepresent invention.

EXAMPLE 1

Over a period of one hour, 4-aminobutyraldehyde dimethyl acetal (22.0 g,0.165 mole) was added dropwise through an addition funnel to a stirredslurry of cyanuric chloride (9.2 g, 0.05 mole), toluene (175 ml), andpowdered potassium hydroxide (8.5 g, 0.152 mole) in a 500 ml flaskequipped with a reflux condenser, thermometer, nitrogen inlet andmechanical stirrer. The reaction mixture was kept under nitrogenthroughout the reaction. The addition rate of the 4-aminobutyraldehydedimethyl acetal was controlled to maintain the reaction temperature ator below 50° C. (exothermic). After the addition was completed, theslurry was heated under reflux for eight hours, then cooled andfiltered. The filtrate was concentrated in vacuo to give a viscous oilwhich was dissolved in ethyl acetate (250 ml), washed with water, driedover anhydrous sodium sulfate, filtered, and the volatiles removed undervacuum to give a viscous oil (20.0 g, 92.8% isolated yield). The oil wasanalyzed by infrared (IR), nuclear magnetic resonance (NMR), and massspectroscopy (MS) and was identified to be the desired2,4,6-tris-(4,4-dimethoxybutylamino)-1,3,5-triazine: IR (neat, cm⁻¹):3354, 3271, 1566, 1519, 1125, 814; ¹ H NMR (δ): 4.4 (t, 1H), 3.4 -3.3(m, 2H), 3.3 (s, 6H), 1.8-1.6(m, 4H); ¹³ C NMR (ppm): 166, 104, 53, 40,30, 25; MS (m/e, MH): 475.

EXAMPLE 2

The procedure of Example 1 was repeated with the exception thataminoacetaldehyde dimethyl acetal (6.3 g, 0.060 mole) and cyanuricchloride (3.68 g, 0.02 mole) were used to give2,4,6-tris-(2,2-dimethoxyethylamino)-1,3,5-triazine as an oily productin 80.8% isolated yield (6.3g). The structure was analyzed by infrared(IR) spectroscopy, and confirmed by NMR spectroscopy ¹ H NMR (δ): 4.2(t, 1H), 3.6-3.2 (m, 2H), 3.4 (s, 6H).

EXAMPLE 3

This example illustrates solvent-based curable coating compositioncontaining the 2,4,6-tris-(4,4-dimethoxybutylamino)-1,3,5-triazine ofExample 1 as the crosslinker, JONCRYL® 500 acrylic resin (S. C. Johnson& Sons) as the polyfunctional material, and CYCAT® 4040 (CytecIndustries Inc.) as the cure catalyst. CYCAT® 4040 cure catalyst is 40weight % para-toluenesulfonic acid in isopropanol. The amount of CYCAT®4040 cure catalyst used corresponded to about 0.3 weight %(solids/solids) based on the polyfunctional material plus crosslinker.Toluene was used as the solvent to adjust the solids level of thecoating composition to 60 weight %.

    ______________________________________                                        COMPOSITION               Weight (g)                                          ______________________________________                                        JONCRYL ® 500 acrylic resin                                                                         6.25                                                2,4,6-tris-(4,4-dimethoxybutylamino)-1,3,5-triazine                                                     1.60                                                CYCAT ® 4040 cure catalyst                                                                          0.05                                                Toluene                   3.10                                                ______________________________________                                    

The curable composition was applied to Bonderite® 1000 panels bydraw-down (40 mil diameter wire cator) and baked at 180° C. for 20minutes to give a cured coating having a pencil hardness of F-HB. Thesolvent resistance was 1/200+ MEK rubs (methyl ethyl ketone double rubsto mar/remove).

EXAMPLE 4

The procedure of Example 3 was repeated with the exception that thecatalyst level was increased to 1 weight % (solids/solids). As before,toluene was used as the solvent to adjust the solids level to 60 weight%.

    ______________________________________                                        COMPOSITION               Weight (g)                                          ______________________________________                                        JONCRYL ® 500 acrylic resin                                                                         6.25                                                2,4,6-tris-(4,4-dimethoxybutylamino)-1,3,5-triazine                                                     1.60                                                CYCAT ® 4040 cure catalyst                                                                          0.17                                                Toluene                   2.98                                                ______________________________________                                    

The composition was applied to Bonderite® 1000 panel by draw-down (40mil diameter wire cator) and baked at 170° C. for 20 minutes to givecured coating with a solvent resistance corresponding to 50/200+ MEKrubs.

EXAMPLE 5

The procedure of Example 4 was repeated with the exception that thecatalyst level was increased to 2 weight % (solids/solids). As before,toluene was used as the solvent to adjust the solids level to 60 weight%.

    ______________________________________                                        COMPOSITION               Weight (g)                                          ______________________________________                                        JONCRYL ® 500 acrylic resin                                                                         6.25                                                2,4,6-tris-(4,4-dimethoxybutylamino)-1,3,5-triazine                                                     1.60                                                CYCAT ® 4040 cure catalyst                                                                          0.34                                                Toluene                   2.81                                                ______________________________________                                    

The composition was applied to Bonderite® 1000 panel by draw-down (40mil diameter wire cator) and baked at 160° C. for 20 minutes to givecured coating with a solvent resistance corresponding to 200 +/200+ MEKrubs. While the panels baked at higher temperature (180° C.) exhibitedsome yellowing, there was no yellowing at 160° C. with the presenthigher catalyst level.

EXAMPLE 6

A solvent based formulation was prepared using the procedure of Example4 with the 2,4,6-tris-(2,2-dimethoxyethylamino)-1,3,5-triazine ofExample 2 as the crosslinker.

    ______________________________________                                        COMPOSITION               Weight (g)                                          ______________________________________                                        JONCRYL ® 500 acrylic resin                                                                         6.25                                                2,4,6-tris-(2,2-dimethoxyethylamino)-1,3,5-triazine                                                     1.30                                                CYCAT ® 4040 cure catalyst                                                                          0.32                                                Toluene                   2.63                                                ______________________________________                                    

The composition was applied to Bonderite® 1000 substrate panel bydraw-down (40 mil diameter wire cator) and baked at 1800° C. for 20minutes. This resulted in a cured coating with 1/200+ MEK rubs with someyellowing.

EXAMPLE 7

A mixture of strongly acidic AMBERLYST® 15 ion-exchange resin (6.6 g), aproduct of Rohm and Haas Company, Philadelphia, Pa., and methylenechloride (20 ml) in a 100 ml flask equipped with a magnetic stirrer,condenser and nitrogen inlet was stirred for 5 minutes and thereafter,the solvent was removed by decanting. A solution of the2,4,6-tris-(4,4-dimethoxybutylamino)-1,3,5-triazine of Example 1 (6.1 g,0.0129 mole) in methylene chloride (120 ml) was then added in oneportion to the flask and the resulting mixture was stirred at roomtemperature under a nitrogen atmosphere for 1.5 hours. The ion exchangeresin was then filtered and the volatiles removed under reduced pressureto give 2,4,6-tris-(2-methoxypyrrolidinyl)-1,3,5-triazine (2.7 g, 56 %isolated yield) as a glassy solid. The structure of the product wasconfirmed by nuclear magnetic resonance (NMR) and mass spectroscopic(MS) analysis: ¹ H NMR (5 ): 5.6 (m, 1 H, --NCHOCH₃); 3.8 -3.2 (m, 5H,--OCH₃ and --NCH₂); 2.2-1.6 (m, 4H,--CH₂ --); ¹³ C NMR (ppm): 165, 88,56, 46, 32, 22; MS (m/e, MH): 379.

EXAMPLE 8

This example illustrates the use of the2,4,6-tris-(2-methoxypyrrolidinyl)-1,3,5-triazine of Example 7 as acrosslinker in a curable solvent based coating composition with JONCRYL®500 acrylic resin and toluene at 60 weight % solids level. No curecatalyst was used in the formulation. The equivalent ratios of OH tocyclic amino-ether was 1/1.

    ______________________________________                                        COMPOSITION               Weight (g)                                          ______________________________________                                        JONCRYL ® 500 acrylic resin                                                                         3.00                                                2,4,6-tris-(2-methoxypyrrolidinyl)-1,3,5-triazine                                                       0.63                                                Toluene                   2.00                                                ______________________________________                                    

The composition was applied to Bonderite® 1000 substrate panel bydraw-down (40 mil diameter wire cator) and baked at 70° C. for 20minutes. The composition cured without yellowing producing a coatinghaving good solvent resistance and hardness. The solvent resistance was200+/200+ MEK rubs and the pencil hardness was F-HB. When baked at 50°C. for 60 minutes, the solvent resistance was 200+/200+ MEK rubs.Similarly, when baked at 50° C. for 20 minutes and thereafter kept atambient temperatures for 13 days, the coating had a solvent resistanceof 200+/200+ MEK rubs.

EXAMPLE 9

Water (50 ml) containing 37 weight % hydrochloric acid (6 ml) was addedin one portion to a stirred solution of thetris-(4,4-dimethoxybutylamino)-1,3,5-triazine of Example 1 (6.0 g;0.0127 mole) in acetone (50 ml) under nitrogen. The reaction mixture wasstirred at room temperature for four days and thereafter neutralizedwith solid potassium carbonate. The solution was then transferred to aseparatory funnel and extracted with ethyl acetate (2×150 ml). Theorganic layer was separated, dried over anhydrous sodium sulfate and thevolatiles were removed under reduced pressure to give2,4,6-tris-(2-hydroxypyrrolidin-1-yl)-1,3,5-triazine as a solid (2.7 g;64% isolated yield). The structure of the product was confirmed from the¹ H NMR spectrum which exhibited the characteristic absorption for the--NCHO- group at (δ) 5.6 (m, 1H).

EXAMPLE 10

This example illustrates the use oft(2,4,6-tris-(2-hydroxypyrrolidinyl)-1,3,5-triazine of Example 9 as acrosslinker in a curable solvent based coating composition with JONCRYL®500 acrylic resin and toluene at 60 weight % solids level. No curecatalyst was used in the formulation. The equivalent ratios of OH tocyclic amino-ether was 1/1.

    ______________________________________                                        COMPOSITION               Weight (g)                                          ______________________________________                                        JONCRYL ® 500 acrylic resin                                                                         3.10                                                2,4,6-tris-(2-hydroxypyrrolidinyl)-1,3,5-triazine                                                       0.56                                                Toluene                   1.44                                                ______________________________________                                    

The composition was applied to Bonderite® 1000 substrate panel bydraw-down (40 mil diameter wire cator) and baked at 150° C. for 20minutes. The composition cured without yellowing producing a coatinghaving good solvent resistance and hardness. The solvent resistance was1/200+ MEK rubs and the pencil hardness was F-HB.

Although the present invention is described with reference to certainpreferred embodiments, it is apparent that modifications and variationsthereof may be made by those skilled in the art without departing fromthe scope of this invention as defined by the appended claims.

We claim:
 1. A coating composition comprising: (a) a crosslinkercomponent comprising a 1,3,5-triazine compound of the formula (I)##STR9## wherein X is selected from the group consisting of hydrogen,halogen, alkyl, aralkyl, aryl, alkoxy, aralkoxy, aryloxy, alkylthio,aralkylthio, arylthio, amido, sulfonamido, sulfonate, amino,heterocyclic N-containing group optionally containing a differentheteroatom in the ring, a group of the formula (II), a group of theformula (Ill), and a group of the formula (IV) ##STR10## wherein A is analkylene group of 1 to 8 carbon atoms,R¹ is selected from the groupconsisting of hydrogen and a hydrocarbyl, R² is selected from the groupconsisting of hydrogen, a hydrocarbyl, --OR⁹ and --SR¹⁰, R³ is selectedfrom the group consisting of hydrogen, a hydrocarbyl, --OR⁹ and --SR¹⁰,and R⁴ is selected from the group consisting of --OR¹¹ and --SR¹²,withthe proviso that at least one of R² and R³ is selected from the groupconsisting of --OR⁹ and --SR¹⁰, ##STR11## wherein D is an alkylene groupof 3 to 8 carbon atoms, R⁵ is selected from the group consisting ofhydrogen, a hydrocarbyl, --OR⁹ and --SR¹⁰, and R⁶ is selected from thegroup consisting of hydrogen, a hydrocarbyl, --OR⁹ and --SR¹⁰,with theproviso that at least one of R⁵ and R⁶ is selected from the groupconsisting of --OR⁹ and --SR¹⁰, ##STR12## wherein Q is an alkylene groupof 2 to 7 carbon atoms, R⁷ is selected from the group consisting ofhydrogen, a hydrocarbyl, --OR⁹ and --SR¹⁰, and R⁸ is selected from thegroup consisting of hydrogen and a hydrocarbyl,wherein each R⁹ isindependently selected from the group consisting of hydrogen and ahydrocarbyl, or together with R¹¹ forms a hydrocarbylene group, each R¹⁰is a hydrocarbyl, or together with R¹² forms a hydrocarbylene group,each R¹¹ is independently selected from the group consisting of hydrogenand a hydrocarbyl, or together with R⁹ forms a hydrocarbylene group,each R¹² is a hydrocarbyl, or together with R¹⁰ forms a hydrocarbylenegroup,with the proviso that, other than in a group of the formula (II),(III) or (IV), X contains no olefinic unsaturation; and wherein each ofY and Z is independently selected from the group consisting of a groupof the formula (II), a group of the formula (III) and a group of theformula (IV); and(b) a polyfunctional material containing on average atleast two groups with active hydrogen functionality and/or functionalityconvertible thereto.
 2. A method of coating a substrate by applying thecoating composition of claim 1 and heat curing the so-applied coating.3. A crosslinked film derived from the coating composition of claim 1.4. The coating composition of claim 1, wherein:X is selected from thegroup consisting of hydrogen, alkyl of 1 to 8 carbon atoms, aryl of 6 to10 carbon atoms, aralkyl of 7 to 14 carbon atoms, alkoxy of 1 to 8carbon atoms, aryloxy of 6 to 10 carbon atoms, aralkoxy of 7 to 14carbon atoms, alkylthio of 1 to 8 carbon atoms, arylthio of 6 to 10carbon atoms, aralkylthio of 7 to 14 carbon atoms, amido of 1 to 8carbon atoms, sulfonamido of 1 to 8 carbon atoms, --NH₂, monoalkylaminoof 1 to 8 carbon atoms, dialkylamino of 2 to 16 carbon atoms,pyrrolidino, piperidino, azepino, morpholino, N-alkylpiperazino, a groupof the formula (II), a group of the formula (III) and a group of theformula (IV); A is an alkylene group of 1 to 8 carbon atoms; R¹ isselected from the group consisting of hydrogen and an alkyl of 1 to 8carbon atoms; R² is selected from the group consisting of hydrogen, analkyl of 1 to 8 carbon atoms and --OR⁹ ; R³ is selected from the groupconsisting of hydrogen, an alkyl of 1 to 8 carbon atoms and --OR⁹ ; R⁴is --OR¹¹ ;with the proviso that at least one of R² and R³ is a group--OR⁹ ; D is an alkylene group of 3 to 8 carbon atoms; R⁵ is selectedfrom the group consisting of hydrogen, an alkyl of 1 to 8 carbon atomsand --OR⁹ ; R⁶ is selected from the group consisting of hydrogen, analkyl of 1 to 8 carbon atoms and --OR⁹ ;with the proviso that at leastone of R⁵ and R⁶ is --OR⁹ ; Q is an alkylene group of 2 to 7 carbonatoms; R⁷ is selected from the group consisting of hydrogen, an alkyl of1 to 8 carbon atoms and --OR⁹ ; R⁸ is selected from the group consistingof hydrogen and an alkyl of 1 to 8 carbon atoms; each R⁹ isindependently selected from the group consisting of hydrogen and analkyl of 1 to 8 carbon atoms, or together with R¹¹ forms an alkylenegroup of 2 to 8 carbon atoms, each R¹¹ is independently selected fromthe group consisting of hydrogen and an alkyl of 1 to 8 carbon atoms, ortogether with R⁹ forms an alkylene group of 2 to 8 carbon atoms,with theproviso that, other than in a group of the formula (II), (Ill) or (IV),X contains no olefinic unsaturation; and each of Y and Z isindependently selected from the group consisting of a group of theformula (II), a group of the formula (III) and a group of the formula(IV).
 5. The coating composition of claim 4, wherein only one of R² andR³ is a group --OR⁹, only one of only one of R⁵ and R⁶ is a group --OR⁹,and R⁷ is selected from hydrogen and an alkyl of 1 to 8 carbon atoms. 6.The coating composition of claim 5, wherein A is an alkylene of 3 to 8carbon atoms, D is an alkylene of 3 to 8 carbon atoms, and Q is analkylene of 2 to 7 carbon atoms.
 7. The coating composition of claim 6,wherein A is an alkylene of 3 to 5 carbon atoms, D is an alkylene of 3to 5 carbon atoms, and D is an alkylene of 2 to 4 carbon atoms.
 8. Thecoating composition of claim 1, wherein for the compound of the formula(I) X is selected from the group consisting of a group of the formula(II), a group of the formula (III) and a group of the formula (IV). 9.The coating composition of claim 8, wherein X, Y and Z are independentlyselected from the group consisting of a group of the formula (II) and agroup of the formula (III).
 10. The coating composition of claim 1,wherein:X is selected from the group consisting of hydrogen, alkyl of 1to 8 carbon atoms, aryl of 6 to 10 carbon atoms, aralkyl of 7 to 14carbon atoms, alkoxy of 1 to 8 carbon atoms, aryloxy of 6 to 10 carbonatoms, aralkoxy of 7 to 14 carbon atoms, alkylthio of 1 to 8 carbonatoms, arylthio of 6 to 10 carbon atoms, aralkylthio of 7 to 14 carbonatoms, amido of 1 to 8 carbon atoms, sulfonamido of 1 to 8 carbon atoms,--NH₂, monoalkylamino of 1 to 8 carbon atoms, dialkylamino of 2 to 16carbon atoms, pyrrolidino, piperidino, azepino, morpholino,N-alkylpiperazino, a group of the formula (II), a group of the formula(Ill) and a group of the formula (IV); A is an alkylene group of 3 to 5carbon atoms; R¹ is selected from the group consisting of hydrogen andan alkyl of 1 to 4 carbon atoms; R² is --OR⁹ ; R³ is selected from thegroup consisting of hydrogen and an alkyl of 1 to 4 carbon atoms; R⁴ is--OR¹¹ ; D is an alkylene group of 3 to 5 carbon atoms; R⁵ is --OR⁹ ; R⁶is selected from the group consisting of hydrogen and an alkyl of 1 to 4carbon atoms; Q is an alkylene group of 2 to 4 carbon atoms; R⁷ isselected from the group consisting of hydrogen and an alkyl of 1 to 8carbon atoms; R⁸ is selected from the group consisting of hydrogen andan alkyl of 1 to 4 carbon atoms; each R⁹ is independently selected fromthe group consisting of hydrogen and an alkyl of 1 to 4 carbon atoms, ortogether with R¹¹ forms an alkylene group of 2 to 8 carbon atoms, eachR¹¹ is independently selected from the group consisting of hydrogen andan alkyl of 1 to 4 carbon atoms, or together with R⁹ forms an alkylenegroup of 2 to 8 carbon atoms,with the proviso that, other than in agroup of the formula (II), (III) or (IV), X contains no olefinicunsaturation; and each of Y and Z is independently selected from thegroup consisting of a group of the formula (II), a group of the formula(III) and a group of the formula (IV).
 11. The coating composition ofclaim 10, wherein X is selected from the group consisting of a group ofthe formula (II), a group of the formula (III) and a group of theformula (IV).
 12. The coating composition of claim 11, wherein X, Y andZ are independently selected from the group consisting of a group of theformula (II) and a group of the formula (III).
 13. A coating compositioncomprising (a) a crosslinker component and (b) a polyfunctional materialcontaining on average at least two groups with active hydrogenfunctionality and/or functionality convertible thereto, wherein thecrosslinker component (a) comprises a composition comprising on averageper molecule at least two groups selected from the group consisting ofgroups of the formula (II), groups of the formula (III) and groups ofthe formula (IV) ##STR13## wherein A is an alkylene group of 1 to 8carbon atoms,R¹ is selected from the group consisting of hydrogen and ahydrocarbyl, R² is selected from the group consisting of hydrogen, ahydrocarbyl, --OR⁹ and --SR ¹⁰, R³ is selected from the group consistingof hydrogen, a hydrocarbyl, --OR⁹ and --SR ¹⁰, and R⁴ is selected fromthe group consisting of --OR¹¹ and --SR¹²,with the proviso that at leastone of R² and R³ is selected from the group consisting of --OR⁹ and--SR¹⁰, ##STR14## wherein D is an alkylene group of 3 to 8 carbon atoms,R⁵ is selected from the group consisting of hydrogen, a hydrocarbyl,--OR⁹ and --SR¹⁰ , and R⁶ is selected from the group consisting ofhydrogen, a hydrocarbyl, --OR⁹ and --SR ¹⁰,with the proviso that atleast one of R⁵ and R⁶ is selected from the group consisting of --OR⁹and --SR¹⁰, ##STR15## wherein Q is an alkylene group of 2 to 7 carbonatoms, R⁷ is selected from the group consisting of hydrogen, ahydrocarbyl, --OR⁹ and --SR¹⁰, and R⁸ is selected from the groupconsisting of hydrogen and a hydrocarbyl,wherein each R⁹ isindependently selected from the group consisting of hydrogen and ahydrocarbyl, or together with R¹¹ forms a hydrocarbylene group, each R¹⁰is a hydrocarbyl, or together with R¹² forms a hydrocarbylene group,each R¹¹ is independently selected from the group consisting of hydrogenand a hydrocarbyl, or together with R⁹ forms a hydrocarbylene group,each R¹² is a hydrocarbyl, or together with R¹⁰ forms a hydrocarbylenegroup, prepared by the step of contacting:(i) a 1,3,5-triazinederivative represented by the formula (V) or an oligomer thereof:##STR16## wherein L¹ is selected from the group consisting of hydrogen,halogen, alkyl, aralkyl, aryl, alkoxy, aralkoxy, aryloxy, alkylthio,aralkylthio, arylthio, amido, sulfonamido, sulfonate, amino and aleaving group not previously mentioned, and each of L² and L³ isindependently a leaving group; and(ii) a nucleophilic reagent selectedfrom the group consisting of a compound of the formula (VI), a compoundof the formula (VII), a compound of the formula (VII), a salt thereofand mixtures thereof: ##STR17## wherein A, R¹, R², R³ and R⁴ are asdefined above, with the proviso that at least one of R² and R³ isselected from the group consisting of --OR⁹ and --SR¹⁰, ##STR18##wherein D, R⁵ and R⁶ are as defined above, with the proviso that atleast one of R⁵ and R⁶ is selected from the group consisting of --OR⁹and --SR¹⁰, ##STR19## wherein Q, R⁷ and R⁸ are as defined above,whereinR⁹ and R¹⁰ are as defined above, and herein said contacting is carriedout at a temperature and length of time sufficient to produce a1,3,5-triazine derivative having thereon on average at least two groupsderived from the nucleophilic reagent.
 14. The coating composition ofclaim 13, wherein:R¹ is selected from the group consisting of hydrogenand an alkyl of 1 to 8 carbon atoms; R² is selected from the groupconsisting of hydrogen, an alkyl of 1 to 8 carbon atoms and --OR⁹ ; R³is selected from the group consisting of hydrogen, an alkyl of 1 to 8carbon atoms and --OR⁹ ; R⁴ is --OR¹ ;with the proviso that at least oneof R² and R³ is a group --OR⁹ ; R⁵ is selected from the group consistingof hydrogen, an alkyl of 1 to 8 carbon atoms and --OR⁹ ; R⁶ is selectedfrom the group consisting of hydrogen, an alkyl of 1 to 8 carbon atomsand --OR⁹ ;with the proviso that at least one of R⁵ and R⁶ is --OR⁹ ; R⁷is selected from the group consisting of hydrogen, an alkyl of 1 to 8carbon atoms and --OR⁹ ; R⁸ is selected from the group consisting ofhydrogen and an alkyl of 1 to 8 carbon atoms; each R⁹ is independentlyselected from the group consisting of hydrogen and an alkyl of 1 to 8carbon atoms, or together with R¹¹ forms an alkylene group of 2 to 8carbon atoms, and each R¹¹ is independently selected from the groupconsisting of hydrogen and an alkyl of 1 to 8 carbon atoms, or togetherwith R⁹ forms an alkylene group of 2 to 8 carbon atoms.
 15. The coatingcomposition of claim 14, wherein only one of only one of R² and R³ is agroup --OR⁹, only one of only one of R⁵ and R⁶ is a group --OR⁹, and R⁷is selected from hydrogen and an alkyl of 1 to 8 carbon atoms.
 16. Thecoating composition of claim 15, wherein A is an alkylene of 3 to 8carbon atoms, D is an alkylene of 3 to 8 carbon atoms, and Q is analkylene of 2 to 7 carbon atoms.
 17. The coating composition of claim16, wherein A is an alkylene of 3 to 5 carbon atoms, D is an alkylene of3 to 5 carbon atoms, and Q is an alkylene of 2 to 4 carbon atoms. 18.The coating composition of claim 13, wherein:A is an alkylene group of 3to 5 carbon atoms; R¹ is selected from the group consisting of hydrogenand an alkyl of 1 to 4 carbon atoms; R² is --OR⁹ ; R³ is selected fromthe group consisting of hydrogen and an alkyl of 1 to 4 carbon atoms; R⁴is --OR¹¹ ; D is an alkylene group of 3 to 5 carbon atoms; R⁵ is --OR⁹ ;R⁶ is selected from the group consisting of hydrogen and an alkyl of 1to 4 carbon atoms; Q is an alkylene group of 2 to 4 carbon atoms; R⁷ isselected from the group consisting of hydrogen and an alkyl of 1 to 8carbon atoms; R⁸ is selected from the group consisting of hydrogen andan alkyl of 1 to 4 carbon atoms; each R⁹ is independently selected fromthe group consisting of hydrogen and an alkyl of 1 to 4 carbon atoms, ortogether with R¹¹ forms an alkylene group of 2 to 8 carbon atoms, andeach R¹¹ is independently selected from the group consisting of hydrogenand an alkyl of 1 to 4 carbon atoms, or together with R⁹ forms analkylene group of 2 to 8 carbon atoms.
 19. A coating compositioncomprising (a) a crosslinker component and (b) a polyfunctional materialcontaining on average at least two groups with active hydrogenfunctionality and/or functionality convertible thereto, wherein thecrosslinker component (a) comprises a composition comprising on averageper molecule at least two groups selected from the group consisting ofgroups of the formula (II) and groups of the formula (III) ##STR20##wherein A is an alkylene group of 1 to 8 carbon atoms,R¹ is selectedfrom the group consisting of hydrogen and a hydrocarbyl, R² is selectedfrom the group consisting of hydrogen, a hydrocarbyl, --OR ⁹ and --SR¹⁰, R³ is selected from the group consisting of hydrogen, a hydrocarbyl,--OR ⁹ and --SR ¹⁰, and R⁴ is selected from the group consisting of--OR¹¹ and --SR¹²,with the proviso that at least one of R² and R³ isselected from the group consisting of --OR⁹ and --SR¹⁰, ##STR21##wherein D is an alkylene group of 3 to 8 carbon atoms, R⁵ is selectedfrom the group consisting of hydrogen, a hydrocarbyl, --OR⁹ and --SR¹⁰,and R⁶ is selected from the group consisting of hydrogen, a hydrocarbyl,--OR ⁹ and --SR¹⁰,with the proviso that at least one of R⁵ and R⁶ isselected from the group consisting of --OR⁹ and --SR¹⁰, herein each R⁹is independently selected from the group consisting of hydrogen and ahydrocarbyl, or together with R¹¹ forms a hydrocarbylene group, each R¹⁰is a hydrocarbyl, or together with R¹² forms a hydrocarbylene group,each R¹¹ is independently selected from the group consisting of hydrogenand a hydrocarbyl, or together with R⁹ forms a hydrocarbylene group,each R¹² is a hydrocarbyl, or together with R¹⁰ forms a hydrocarbylenegroup, prepared by the steps of(A) contacting (i) a 1,3,5-triazinederivative represented by the formula (V) or an oligomer thereof##STR22## wherein L¹ is selected from the group consisting of hydrogen,halogen, alkyl, aralkyl, aryl, alkoxy, aralkoxy, aryloxy, alkylthio,aralkylthio, arylthio, amido, sulfonamido, sulfonate, amino and aleaving group not previously mentioned, and each of L² and L³ isindependently a leaving group; and(ii) a nucleophilic reagent of theformula (VI) or a salt thereof, ##STR23## wherein A, R¹, R², R³ and R⁴are as defined above, with the proviso that at least one of R² and R³ isselected from the group consisting of --OR⁹ and --SR¹⁰, wherein R⁹ andR¹⁰ are as defined above, at a temperature and for a length of timesufficient to produce a 1,3,5-triazine derivative having thereon onaverage at least two open-chain groups derived from the nucleophilicagent; then (B) intramolecularly cyclizing at least a portion of theopen-chain groups to groups of the formula (III).
 20. The coatingcomposition of claim 19, wherein:R¹ is selected from the groupconsisting of hydrogen and an alkyl of 1 to 8 carbon atoms; R² isselected from the group consisting of hydrogen, an alkyl of 1 to 8carbon atoms and --OR⁹ ; R³ is selected from the group consisting ofhydrogen, an alkyl of 1 to 8 carbon atoms and --OR⁹ ; R⁴ is --OR¹¹ ;withthe proviso that at least one of R² and R³ is a group --OR⁹ ; R⁵ isselected from the group consisting of hydrogen, an alkyl of 1 to 8carbon atoms and --OR⁹ ; R⁶ is selected from the group consisting ofhydrogen, an alkyl of 1 to 8 carbon atoms and --OR⁹ ;with the provisothat at least one of R⁵ and R⁶ is --OR⁹ ; each R⁹ is independentlyselected from the group consisting of hydrogen and an alkyl of 1 to 8carbon atoms, or together with R¹¹ forms an alkylene group of 2 to 8carbon atoms, and each R¹¹ is independently selected from the groupconsisting of hydrogen and an alkyl of 1 to 8 carbon atoms, or togetherwith R⁹ forms an alkylene group of 2 to 8 carbon atoms.
 21. The coatingcomposition of claim 20, wherein only one of only one of R² and R³ is agroup --OR⁹, and only one of only one of R⁵ and R⁶ is a group --OR⁹. 22.The coating composition of claim 21, wherein A is an alkylene of 3 to 8carbon atoms, and D is an alkylene of 3 to 8 carbon atoms.
 23. Thecoating composition of claim 22, wherein A is an alkylene of 3 to 5carbon atoms, and D is an alkylene of 3 to 5 carbon atoms.
 24. Thecoating composition of claim 19, wherein:A is an alkylene of 3 to 5carbon atoms; R¹ is selected from the group consisting of hydrogen andan alkyl of 1 to 4 carbon atoms; R² is --OR⁹ ; R³ is selected from thegroup consisting of hydrogen and an alkyl of 1 to 4 carbon atoms; R⁴ is--OR¹¹ ; D is an alkylene of 3 to 5 carbon atoms; R⁵ is --OR⁹ ; R⁶ isselected from the group consisting of hydrogen and an alkyl of 1 to 4carbon atoms; each R⁹ is independently selected from the groupconsisting of hydrogen and an alkyl of 1 to 4 carbon atoms, or togetherwith R¹¹ forms an alkylene group of 2 to 8 carbon atoms, and each R¹¹ isindependently selected from the group consisting of hydrogen and analkyl of 1 to 4 carbon atoms, or together with R⁹ forms an alkylenegroup of 2 to 8 carbon atoms.
 25. A method of coating a substrate byapplying the coating composition of claim 13 and heat curing theso-applied coating.
 26. A method of coating a substrate by applying thecoating composition of claim 19 and heat curing the so-applied coating.27. A crosslinked film derived from the coating composition of claim 13.28. A crosslinked film derived from the coating composition of claim 19.